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CN1343023A - lithium-based battery - Google Patents

lithium-based battery Download PDF

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Publication number
CN1343023A
CN1343023A CN01137247A CN01137247A CN1343023A CN 1343023 A CN1343023 A CN 1343023A CN 01137247 A CN01137247 A CN 01137247A CN 01137247 A CN01137247 A CN 01137247A CN 1343023 A CN1343023 A CN 1343023A
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CN
China
Prior art keywords
battery
structure group
battery structure
element cell
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN01137247A
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Chinese (zh)
Inventor
佐藤贵哉
吉田浩
桥本善三
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Itochu Corp
Original Assignee
Itochu Corp
Nisshinbo Industries Inc
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Filing date
Publication date
Application filed by Itochu Corp, Nisshinbo Industries Inc filed Critical Itochu Corp
Publication of CN1343023A publication Critical patent/CN1343023A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/42—Grouping of primary cells into batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Primary Cells (AREA)

Abstract

A lithium-based battery includes a battery structure group made by stacking unit cells each including a positive electrode, a negative electrode, and a separator disposed therebetween, or made by repeatedly folding or winding the unit cells in one piece, a battery container for accommodating the battery structure group, and an electrolyte injected into the battery container after the battery structure group is mounted in the battery container. The outer peripheral surface of the battery container is covered with an ion-impermeable and extensible polymer sheet having a tensile elongation of 1% or more. According to this configuration, even when an accident occurs due to an external cause, i.e., a nail penetrates the battery or the battery is broken, a large short-circuit current is prevented from flowing between the positive electrode and the negative electrode, thereby ensuring high safety of the battery.

Description

Lithium-base battery
Technical field
The present invention relates to a kind of can be with the lithium-base battery of high security operation, as lithium secondary battery or lithium rechargeable battery.
Background technology
Non-aqueous secondary batteries is assembled by following method: prepare a kind of battery structure group, this battery structure group forms by stacked unit cells, each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film, and perhaps this battery structure group is the integral body preparation by the winder unit battery; This battery structure group is installed in the battery case; And fill this battery case with nonaqueous electrolyte.In addition, positive pole is made by positive electrode active materials such as cobalt acid lithium (lithium cobaltate) is supported on current collector such as aluminium foil, and negative pole is made by negative active core-shell material such as graphite are supported on current collector such as the Copper Foil.
Above-mentioned rechargeable nonaqueous electrolytic battery adopts a kind of reactivity to be higher than the material of aqueous electrolyte secondary cell, therefore must operate under the situation that its safety measure is paid special attention to.Consider from this angle, for example, disclosing provides a kind of safety valve to discharge the method (1) of gases at high pressure from battery case inside, use the method (2) of PTC device, with use to turn-off barrier film so that the method (3) (referring to Japanese Patent Application Publication 2000-58065,2000-100408 and 2000-133236) of restriction electric current under the situation of short circuit or internal short-circuit externally.
The PTC equipment that in method (2), has PTC (positive temperature coefficient) characteristic can make resistance along with battery in temperature rising and become big, thereby electric current passes through during the restriction external short circuit.Shutoff barrier film in the method (3), fusion when it is at high temperature heated, thus make it lose the ion impermeability.Therefore, be inserted between the electrode if will turn-off barrier film, externally when short circuit or internal short-circuit, the electric current that it can limit between the electrode flows.
By the way, if sharp as shown in figure 16 metal bar such as nail pierce through battery, this metal bar penetrates positive pole 1 and barrier film 3, and arrives negative pole 2.Consequently, anode collection device 1a directly contacts with this metal bar 9 with positive electrode active materials, and negative pole currect collecting device 2a directly contacts with this metal bar 9 with negative active core-shell material, and therefore anodal 1 by this metal bar 9 and negative pole 2 internal short-circuits.In such cases, because electric current only flows in battery, of no use with the PTC equipment current limliting in the method (2), and the shutoff barrier film in the method (3) can not prevent to pierce through moment of electrode 1 and 2 when metal bar 9 by barrier film 3, big electric current anodal 1 and negative pole 2 between flow.
When battery crushing, barrier film 3 can break usually, thereby causes the short circuit between positive pole 1 and the negative pole 2.In the case, the PTC equipment in the method (2) is of no use, and the shutoff barrier film in the method (3) can not prevent to pierce through moment of electrode 1 and 2 when metal bar 9 by barrier film 3, big electric current anodal 1 and negative pole 2 between flow.
In this manner, the shortcoming of prior art battery is, if when causing serious accident takes place owing to outside cause, for example, when if nail pierces through battery or battery crushing, very large short circuit current moment flows between electrode, and this makes battery be in the high temp/high pressure state, consequently has battery to be lighted and/or the danger of explosion.Therefore, there is the problem of the safety that can not keep enough in the prior art battery.
Summary of the invention
An object of the present invention is to provide a kind of lithium-base battery, as lithium secondary battery or lithium rechargeable battery, even when causing serious accident takes place owing to outside cause, when for example nail pierces through battery or battery crushing, it can prevent that also big electric current from flowing through between the electrode, thereby has improved fail safe.
To achieve these goals, according to a first aspect of the invention, provide a kind of lithium-base battery, having comprised: the battery structure group, this battery structure group is made by stacked unit cells.Each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film that perhaps this battery structure group is by the integral body preparation of folding or winder unit battery; Battery case is used to hold this battery structure group; And electrolyte, after the battery structure group is installed in the battery case, be injected in the battery case; Wherein the outer surface of battery case is coated with ion impermeable and extendible high polymer sheet, and its stretch percentage elongation is 1% or bigger.
According to a second aspect of the invention, provide a kind of lithium-base battery, having comprised: the battery structure group, this battery structure group is made by stacked unit cells.Each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film that perhaps this battery structure group is by the integral body preparation of folding or winder unit battery; And electrolyte; Wherein the periphery of battery structure group is coated with ion impermeable and extendible high polymer sheet, and its stretch percentage elongation is 1% or bigger.
According to a third aspect of the invention we, provide a kind of lithium-base battery, having comprised: the battery structure group, this battery structure group is made by stacked unit cells.Each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film that perhaps this battery structure group is by the integral body preparation of folding or winder unit battery; Battery case is used to hold this battery structure group; And electrolyte, after the battery structure group is installed in the battery case, be injected in the battery case; Wherein the outer surface of battery case is coated with ion impermeable and extendible high polymer sheet, and its stretch percentage elongation is 1% or bigger, and the periphery of battery structure group also is coated with this ion impermeable and extendible high polymer sheet.
According to a forth aspect of the invention, provide a kind of lithium-base battery, having comprised: the battery structure group, this battery structure group is made by stacked unit cells.Each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film that perhaps this battery structure group is by the integral body preparation of folding or winder unit battery; Battery case is used to hold this battery structure group; And electrolyte, after the battery structure group is installed in the battery case, be injected in the battery case; Wherein the positive pole of each element cell and negative pole form in opposed facing mode on a surface of anode collection device and negative pole currect collecting device respectively, and barrier film is set therebetween; And stretch percentage elongation is 1% or bigger ion impermeable and extendible high polymer sheet, is arranged between two adjacent element cells and/or is arranged on the outer surface of each element cell.
According to a fifth aspect of the invention, except the above-mentioned first lithium-base battery structure that either side is described to the third aspect, the positive pole of each element cell and negative pole are forming in opposed facing mode on the surface of anode collection device and on the surface of negative pole currect collecting device respectively.And be provided with barrier film therebetween; And stretch percentage elongation is 1% or bigger ion impermeable and extendible high polymer sheet, is arranged between two adjacent element cells and/or is arranged on the outer surface of each element cell.
According to a sixth aspect of the invention, the lithium-base battery structure that either side is described in above-mentioned first to the 5th aspect, wherein said extensible high polymer sheet is selected from by at least a: polyamide-based elastomer, polyurethane-base elastomer, polyolefin-based elastomer, polyester-based elastomer, styrene-based elastomer, chlorovinyl elastomer and fluorine-based elastomeric material are made.
The present invention has following effect as described above:
Lithium-base battery of the present invention is characterized in that, comprises the battery structure group, and this battery structure group is made by stacked unit cells.Each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film that perhaps this battery structure group is by the integral body preparation of folding or winder unit battery; Battery case is used to hold this battery structure group; And electrolyte, after the battery structure group is installed in the battery case, be injected in the battery case, wherein the outer surface of battery case is coated with ion impermeable and extendible high polymer sheet, and its stretch percentage elongation is 1% or bigger; The periphery of battery structure group is coated with this ion impermeable and extendible high polymer sheet; And/or this extendible high polymer sheet is arranged between two adjacent element cells and/or is arranged on the outer surface of each element cell.Therefore, if because outside cause causes taking place serious accident, for example, if nail pierces through battery or battery crushing, distortion effectively takes place in the high polymer sheet between positive pole and negative pole, flow between electrode to prevent big electric current, thereby prevent that battery is in the high temp/high pressure state, consequently, can prevent battery explosion and/or light.In this manner, according to the present invention, can provide a kind of lithium-base battery that improves fail safe, as lithium secondary battery or lithium rechargeable battery.
In addition, according to the present invention, the outer surface of battery case is coated with the extensible high polymer sheet with high stretch percentage elongation; The periphery of battery structure group is coated with extensible high polymer sheet; And/or this extensible high polymer sheet is arranged between two adjacent element cells and/or is arranged on the outer surface of each element cell, therefore can protect the corner part of battery, and battery structure group and/or element cell can advantageously be fixed.
Description of drawings
Fig. 1 is the schematic cross-section according to the lithium-base battery of first embodiment of the present invention;
Fig. 2 is the schematic cross-section of an element cell of lithium-base battery shown in Figure 1;
Fig. 3 is the schematic cross-section that is used to illustrate the battery structure group of assembling lithium-base battery shown in Figure 1;
Fig. 4 is the battery structure group schematic cross-section according to the lithium-base battery of second embodiment of the invention;
Fig. 5 is the battery structure group schematic cross-section according to another lithium-base battery of second embodiment of the invention;
Fig. 6 A is the perspective view according to the battery structure group of another lithium-base battery of second embodiment of the invention, and Fig. 6 B is the state schematic cross-section that the battery structure group outer surface among the displayed map 6A is coated with extensible high polymer sheet;
Fig. 7 is the schematic cross-section according to the lithium-base battery of the combination of first and second embodiments;
Fig. 8 is the schematic cross-section according to the lithium-base battery of third embodiment of the invention;
Fig. 9 is the schematic cross-section according to another lithium-base battery of third embodiment of the invention;
Figure 10 is the schematic cross-section of an element cell of each battery in the battery shown in Fig. 8 and 9;
Figure 11 A～11C is the perspective view according to three convoluted lithium-base batteries of third embodiment of the invention;
Figure 12 is the perspective view of stacked batteries;
Figure 13 is the perspective view of folded form battery;
Figure 14 is the perspective view of winding type battery;
Figure 15 is the partial section that nail pierces through the state of battery of the present invention; And
Figure 16 is the partial section that nail pierces through the state of prior art battery.
Detailed description of the preferred embodiments
The preferred embodiment of the invention will be described with reference to the accompanying drawings hereinafter.
＜the first embodiment 〉
Fig. 1 is the schematic cross-section according to the lithium-base battery C of first embodiment of the invention; Fig. 2 is the schematic cross-section of element cell T; And Fig. 3 is the schematic cross-section of assembling of the battery structure group M of this lithium-base battery of explanation.
Referring to Fig. 1, obtain by following method according to the lithium-base battery C of first embodiment, be about to element cell T and be stacked one by one to form battery structure group M, wherein each element cell contains anodal 1, negative pole 2 and is arranged at therebetween barrier film 3; Battery structure group M is installed in the battery case 6; Fill battery case 6 with electrolyte; And be 1% or bigger ion does not see through and the outer surface of extendible high polymer sheet 7 clad battery containers 6 with stretch percentage elongation.As shown in Figure 1, anode collection device 1a links to each other with thin slice 10 as positive terminal, and negative pole currect collecting device 2a links to each other with another thin slice 10 as negative terminals.
Can be configured to the electrode type of two-sided coatings as the positive pole 1 (negative pole 2) of the necessary parts of element cell T, wherein two electrodes partly are coated on two surfaces of anode collection device 1a (negative pole currect collecting device 2a), as shown in Figure 2, perhaps be configured to the electrode type of one-sided coating, one of them electrode partly is coated on the surface of anode collection device 1a (negative pole currect collecting device 2a), shown in the reference number among Fig. 38.According to first embodiment, as shown in Figure 3, electrode structure group M makes by piling up the one-sided T of three blade units, and in the electrode body 8 of the highest part and two one-sided electrode coated types of lowermost portion.Under this situation, the relation of arranging between positive pole and the negative pole can be put upside down.Although as shown in figs. 1 and 3, in this embodiment the one-sided T of three blade units is stacked, the element cell number that piles up is not limited to this, and can be one or more.Though not shown, battery structure group M can prepare by folding element cell T.
Battery case 6 is by the packaging material preparation, and its example preferably includes metal forming, as aluminium or stainless paper tinsel, and the lamination high-polymer membrane with sufficient intensity.
This lamination high-polymer membrane preferably layer of polyester, polypropylene, polyethylene, nylon, the nylon that orientation is arranged and the aluminium foil by suitably piling up three～five strata esters, biaxial orientation is made.
Lithium-base battery of the present invention is characterised in that, the outer surface of battery case 6 be coated with stretch percentage elongation be 1% or bigger ion do not see through and extendible high polymer sheet 7.According to the present invention, in order to improve the stretch percentage elongation as the lamination high-polymer membrane of the packaging material that form battery case 6, the one deck in the laminated multi-layer high-polymer membrane can be made by the extendible high polymer sheet of the present invention at least.
The stretch percentage elongation of the extensible high polymer sheet 7 of the present invention is 1% to cross greatlyyer, is preferably 30% or bigger, more preferably 100% or bigger, also be preferably 150% or bigger, and most preferably be 200% or bigger.The upper limit of this stretch percentage elongation is not particularly limited, but is preferably set to 1500%.When the stretch percentage elongation of the high polymer sheet of clad battery container is too small, if when causing meeting accident accident owing to outside cause, for example, when if nail pierces through battery, distortion effectively can not take place in this high polymer sheet between adjacent positive pole and negative pole, thereby allow big electric current moment to flow through betwixt, cause battery to be in the high temp/high pressure state, consequently battery may explosion and/or is lighted.
The above-mentioned stretch percentage elongation of extensible high polymer sheet 7 is values of measuring down at " tensile test method of vulcanized rubber (Tensile Testing Method for Vulcanized Rubber) ", sees JISK6251-1993 for details.The tensile test method that is used to test extensible high polymer sheet 7 is undertaken by following method, promptly prepare No.7 dumb-bell shape test pieces, in strain rate is to make test pieces generation strain under 100 ± 10mm/min, measures the measuring length when rupturing, and determines stretch percentage elongation based on following relational expression.In addition, the measurement of the stretch percentage elongation of extensible high polymer sheet 7 is to carry out under the condition of normal temperature state (23 ± 2 ℃), sees JISK7100 for details; Yet even in the operating temperature range of battery, the stretch percentage elongation of extensible high polymer sheet 7 also can remain in the above-mentioned scope, that is to say, in-20 ℃～80 ℃ temperature range.
The stretch percentage elongation of breakaway poing (%)=[(measuring length of breakaway poing (mm)-measuring length (mm))/measuring length (mm)) * 100
Extensible high polymer sheet 7 of the present invention has the ion impermeability, and preferably it has other performance, as insulation, heat-resisting and gas impermeability.Term used herein " ion impermeability " refers to the high polymer sheet with ion impermeability only almost not to be had or only allows a small amount of ion from wherein passing through, more particularly, referring to the high polymer sheet with ion impermeability does not allow to make the ion of battery-operated quantity to pass through.The structure that adopts battery case 6 outer surfaces to have extensible high polymer sheet 7 can prevent because the contingency of piercing through battery or cell fracture such as nail causes the battery explosion and/or lights, and do not use the conventional extensible barrier film of the ion permeability with hole.The thickness of this extensible high polymer sheet 7 is usually in about 30 μ m～1mm scope.
This extensible high polymer sheet 7 can be by one or both or more kinds of being selected from: polyamide-based elastomer, polyurethane-base elastomer, polyolefin-based elastomer, polyester-based elastomer, styrene-based elastomer, chlorovinyl elastomer and fluorine-based elastomeric material are made.In these materials, styrene-based elastomer, polyolefin-based elastomer, polyurethane-base elastomer and fluorine-based elastomer are preferred, and polyurethane-base elastomer and fluorine-based elasticity originally are most preferred.
Styrene-based elastomer contains polystyrene as hard chain segment, and contains polybutadiene, polyisoprene, hydrogenated butadiene polymer, hydrogenated polyisoprene or hydrogenated butadiene (or styrene-butadiene) rubber as soft rubber.
Polyolefin-based elastomer contains polypropylene or polyethylene as hard chain segment, and contain ethylene-propylene base rubber (EPDM, EPM, EBM), or hydrogenated butadiene (or styrene-butadiene) rubber is as soft segment, its elasticity originally has 300～600% good stretch percentage elongation, and has the good mouldability that is enough to make elastomer formation film shape.
The polyester-based elastomer contains polyester as hard chain segment, and contains polyethers or polyester as soft segment, and this elastomer has wide operating temperature range.
The polyamide-based elastomer contains polyamide as hard chain segment, and contains polyester or polyethers as soft segment.
The chlorovinyl elastomer contains crystalline poly vinyl chloride as hard chain segment, and contains amorphous PVC or acrylonitrile-butadiene rubber (NBR) as soft segment.
The polyurethane-base elastomer contains the carbamic acid ester structure as hard chain segment, and contains polyester or polyethers as soft segment, and this elasticity originally has 400～1200% good stretch percentage elongation, and has and be enough to make elastomer to form the good mouldability of film shape.
Fluorine-based elastomer contains fluororesin as hard chain segment, and contains fluoro-rubber as soft segment, and this elasticity originally has 400～1200% good stretch percentage elongation, and has the good mouldability that is enough to make elastomer formation film shape.
As extensible high polymer sheet, the polyurethane-base elastomer is preferred.More particularly, the thermoplastic polyurethane based elastomeric that is used for extensible high polymer sheet is by (A) a kind of long-chain polyhydric alcohol compound, (B) a kind of chain lengthening agent and (C) a kind of polyisocyanate compounds as the sudden reaction of major constituent preparation.This elastomer is by the amino-formate bond polymerization in molecule.
Number-average molecular weight as the long-chain polyhydric alcohol compound of component (A) is preferably 1000～5000, and more preferably 1500～3000.If the number-average molecular weight of this long-chain polyhydric alcohol compound is too little; the physical property of the polyurethane film of Huo Deing then; as thermal endurance and stretch percentage elongation; usually can degenerate; if and this molecular weight is too high; then raise, and produce the stability that obtains in the thermoplastic polyurethane based elastomeric process and can reduce usually in the building-up process medium viscosity.The number-average molecular weight that should be noted that the long-chain polyhydric alcohol compound refers to the number-average molecular weight that calculates based on the hydroxyl value that is recorded by JISK1577.
Example as the long-chain polyhydric alcohol compound of (A) component comprises (1) polyester-polyalcohol and (2) polyethers-polyalcohol.
Polyester-polyalcohol (1) is by making dicarboxylic acids as poly-(1,4-butylene adipate ester), poly-(1,6-hexane adipate ester), polycaprolactone, adipic-or phthalic acid and aklylene glycol are as ethylene glycol or diethylene glycol (DEG) reaction acquisition.
The example that is used to prepare the polybasic carboxylic acid component of polyester-polyalcohol (1) can comprise: carbon number is 5～15 linear aliphatic dicarboxylic acids, as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid or dodecanedicarboxylic acid; Carbon number is 5～14 side chain aliphatic dicarboxylic acid, as 2-methylsuccinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methylglutaric acid, 2-methyl suberic acid, 3,8-dimethyl decanedioic acid or 3,7-dimethyl decanedioic acid; Aromatic dicarboxylic acid is as terephthalic acid (TPA), M-phthalic acid or phthalic acid; And the derivative of esterification.Above-mentioned material can use separately, or two or more are used in combination.In these materials, carbon number is that 5～14 line style or side chain aliphatic dicarboxylic acid are preferred, more preferably adipic acid, azelaic acid or decanedioic acid.If desired, above-mentioned dicarboxylic acids can be used in combination with a spot of a kind of polybasic carboxylic acid with three or more functional groups.Can use tricarboxylic acids as this kind polybasic carboxylic acid, as 1,2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid.Above-mentioned tricarboxylic acids can use separately or two or more are used in combination.
The example that is used to prepare the polyol component of polyester-polyalcohol (1) can comprise: carbon number is 2～14 linear aliphatic dihydroxylic alcohols, as ethylene glycol, 1, ammediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol or 1,10-decanediol; Carbon number is 3～14 side chain aliphatic dihydric alcohol, as the 2-methyl isophthalic acid, and ammediol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol or 2-methyl isophthalic acid, 8-ethohexadiol; And the alicyclic ring dihydroxylic alcohols, as cyclohexanedimethanol or cyclohexanediol.These materials can use separately or two or more being used in combination.Particularly, carbon number is that 4～10 side chain aliphatic diol is preferred, and the 3-methyl isophthalic acid, and the 5-pentanediol is preferred.
If desired, above-mentioned dihydroxylic alcohols can be used in combination with a spot of polyalcohol with three or more functional group.The example of this kind polyalcohol can comprise: glycerol, trimethylolpropane, butantriol, hexanetriol, tri hydroxy methyl butane, trihydroxy methyl pentane or pentaerythrite.These materials can use separately or two or more are used in combination.Particularly, trimethylolpropane is preferred.
The example of polyethers-polyalcohol (2) can comprise: polyethylene glycol, polypropylene glycol, EO/PO copolymer and polyoxy tetramethylene glycol.These materials can use separately or two or more are used in combination.
As the chain lengthening agent of component (B), preferably use low molecular weight compound, wherein in molecule, exist two can with the reactive hydrogen atom of isocyanate groups reaction, and this molecular weight 300 or lower scope in.
The example of this low molecular weight compound can comprise: aliphatic diol, as ethylene glycol, diethylene glycol (DEG), 1, ammediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol or 1,9-nonanediol; Aromatic diol or alicyclic diol, as 1, two (β-hydroxy ethoxy) benzene, 1 of 4-, 4-cyclohexanediol, two (beta-hydroxyethyl) terephthalate or benzene dimethanol; Diamines is as hydrazine, ethylenediamine, hexamethylene diamine, propane diamine, benzene dimethylamine, IPD, piperazine, bridged piperazine derivatives, phenylenediamine or toluenediamine; And amino alcohol, as adipic acid hydrazides or M-phthalic acid hydrazides.These materials can use separately or two or more are used in combination.
Example as the polyisocyanate compound of component (C) can comprise: aromatic diisocyanates such as toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, to phenylene vulcabond, 1,5-naphthalene diisocyanate, 3-3 '-two chloro-4,4 '-methyl diphenylene diisocyanate or xylylene diisocyanate; And aliphatic series or alicyclic diisocyanate, as hexamethylene diisocyanate, IPDI, 4, the xylylene diisocyanate of 4 '-dicyclohexyl methyl hydride diisocyanate or hydrogenation.These materials can use separately or two or more are used in combination.Polyisocyanate compound can be used in combination with a spot of polyisocyanate compound with three or more functional group, for example, and triphenylmethane triisocyanate.
According to the present invention, preferably, with 1～200 mass parts, be preferably of the chain lengthening agent of 5～100 mass parts as component (B), and with 5～200 mass parts, be preferably the polyisocyanate compounds of 20～100 mass parts, join in the long-chain polyhydric alcohol compound as component (A) of 100 mass parts as component (C).
The method that the present invention prepares the thermoplastic polyurethane based elastomeric is not particularly limited, but can be by mixing long-chain polyhydric alcohol compound as component (A), chain lengthening agent as component (B), as the polyisocyanate compound of component (C) and other required component, and under the urethane catalyst effect, use known urethane reaction technology according to prepolymer technology or one step completed technology, make the mixture urethane that obtains.Particularly, preferably under the condition that does not have solvent substantially, carry out the method for melt polymerization, and more preferred by using the multiaxis screwe-type xtruder to carry out the method for continuous fusion polymerization.
As urethane catalyst, preferably use the tinbase urethane catalyst.The example of tinbase formic acid esters catalyst can comprise: dibutyltin diacetate, dibutyl tin laurate, two (3-mercaptopropionic acid ethyoxyl butyl ester) dibutyl pink salt.The addition of this urethane catalyst (being scaled the amount of tin atom) is preferably 5ppm or littler.If the addition of urethane catalyst is greater than 5ppm, the ability drop of heat-resisting water, heating and the steam under the polyurethane elastomer high temperature of Huo Deing then.
Thermoplastic polyurethane based elastomeric about acquisition like this, its weight average molecular weight is preferably in 5000～500000 scopes, more preferably in 10000～300000 scopes, and its nco index ([NCO]/[OH]) can be preferably 1.0～1.03 in 0.95～1.05 scope.In addition, this nco index is the ratio of OH group (active hydrogen group) total mole number of the molal quantity of NCO group of polyisocyanate compounds and long-chain polyhydric alcohol.
With the thermoplastic polyurethane based elastomeric that so obtains by melt extruding (film is extruded) method or solvent casting method is made membranaceous.
According to melt extruding (film is extruded) method, this thermoplastic polyurethane based elastomeric heats under its fusing point or higher temperature, and remains on this temperature so that fusion is extruded from T mouth mould or gap nozzle, and stretches as required, and cooling.Obtain the film that thickness is about 20 μ m～1mm thus.
According to solvent casting method, this thermoplastic polyurethane based elastomeric is dissolved in can dissolves in this elastomeric solvent, and by scraping blade or drawdown rod with resulting solution casting in flat substrate, then with solvent evaporation, form the film shape thus.
In extensible high polymer sheet, this polyurethane-base elastomer is preferred.
This extensible high polymer sheet is preferably that ion do not see through.It is low that this ion impermeability refers to ionic conductivity.Therefore, if be used as barrier film between the electrode, then can not prepare battery by this ion is not placed through sheet.
The conductivity of preferred extensible high polymer sheet is up to 1 * 10 at 25 ℃ -6S/cm.This conductivity is measured according to following method.Under 25 ℃, should extensible high polymer sheet impregnated in and contain 1MLiClO 4The polypropylene carbonate ester solution in 24 hours.After this, the sheet of expansion is arranged between two stainless steel substrates, to measure ionic conductivity by the composite impedance method down at 25 ℃.
This ion does not see through sheet and does not so expand in organic bath.Therefore, when being immersed in, this sheet contains 1MLiClO under 20 ℃ 4The polypropylene carbonate ester solution in 24 hours, then will invest the lip-deep solution removal of sheet after, when measuring expansion rate, this sheet will have and be up to 130% expansion rate.
Used extensible high polymer sheet has and is up to 1 * 10 among the present invention -6The ionic conductivity of S/cm, and/or be up to 130% expansion rate.
Expansion rate (%)=[, contain 1MLiClO being dipped at 20 ℃ 4The polypropylene carbonate ester solution in the weight (g) of 24 hours rear panels]/[weight (g) of dipping anter]
As shown in Figure 1, lithium-base battery of the present invention has and conventional lithium-base battery identical construction, and different is that the outer surface of battery case 6 is coated with extensible high polymer sheet 7.That is to say, as mentioned above, lithium-base battery of the present invention comprises: the battery structure group, this battery structure group prepares by stacked unit cells T, that each element cell T has is anodal 1, negative pole 2 and be arranged at therebetween barrier film 3, perhaps this battery structure group prepares (the element cell T that just, grows size) by integral body folding or winder unit battery T.
Anodal 1 preferably by on any surface of anode collection device 1a or apply the doping in positive electrode thing prepare on each surface of preceding and rear surface.This doping in positive electrode thing contains adhesive resin, positive electrode active materials and electric conducting material.
This anode collection device 1a can be by the material preparation that is selected from stainless steel, aluminium, titanium, tantalum and nickel.In these materials, consider that from performance and economic favourable angle aluminium is preferred.Shape to current collector is not particularly limited.For example, current collector can be with paper tinsel, wire netting (expanded metal), plate, foam, wool fabric, three-dimensional structure, uses as the shape of net etc.
The example of adhesive resin can comprise: fluorine-based polymer, polyvinylidene fluoride (PVDF) for example, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoro ethlyene dichloride (CTFE) copolymer [P-(VDF-CTFE)], vinylidene fluoride-hexafluoropropylene fluoro rubber, vinylidene fluoride-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) fluorubber, vinylidene fluoride-tetrafluoroethylene-perfluoroalkyl vinyl ether fluorubber; And PPOX, polyethylene, polystyrene, polybutadiene, butyl rubber, nitrile rubber, styrene butadiene rubbers, PBR, poly-sour rubber, nitrocellulose, the polysaccharide of cyanoethylation, as cyanethyl cellulose, polysaccharide derivates and various latex.These materials can use separately or be used in combination with two or more.
Positive electrode active materials can suitably be selected according to the purposes of electrode or the kind of battery.The example that is used for the positive electrode active materials of cathode plate for lithium secondary battery can comprise: contain the compound of I family metal, as CuO, Cu 2O, Ag 2O, CuS or CuSO 2The compound that contains IV family metal is as TiS, SiO 2Or SnO; The compound that contains V family metal is as V 2O 5, V 6O 13, VO x, Nb 2O 5, Bi 2O 3Or Sb 2O 3The compound that contains VI family metal is as CrO 3, Cr 2O 3, MoO 3, MoS 2, WO 3Or SeO 2The compound that contains VII family metal is as MnO 2Or Mn 2O 4The compound that contains VIII family metal is as Fe 2O 3, FeO, Fe 3O 4, Ni 2O 3, NiO or CoO 2And the conduction high polymer compound, be sill as polypyrrole, polyaniline, polyparaphenylene, polyacetylene or polyacene.
The positive electrode active materials that is used for lithium ion secondary battery positive electrode can exemplify: can absorb/discharge chalcogen (chalcogen) compound of lithium ion or contain the chalcogen compound of lithium ion.
This example that can absorb/discharge the chalcogen compound of lithium ion can comprise: FeS 2, TiS 2, MoS 2, V 2O 5, V 6O 13And MnO 2
The example that contains the chalcogen compound of lithium ion can comprise: LiCoO 2, LiMnO 2, LiMn 2O 4, LiMo 2O 4, LiV 3O 8, LiNiO 2, Li xNi yM 1-yO 2(M is one or more metals that are selected from Co, Mh, Ti, Cr, V, Al, Sn, Pb and Zn at least, and x is in 0.05≤x≤1.10 scopes, and y is in 0.5≤y≤1.0 scopes).
The example of electric conducting material can comprise: carbon black, cigarette (ketjen) are black, acetylene black, carbon palpus, carbon fiber, native graphite and Delanium.Dispersant can be joined in the electric conducting material as required.The example of dispersant can comprise: polar solvent, and as N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl formamide, dimethylacetylamide and dimethyl methyl acid amides (dimethylsulfoamide).
Can form the doping in positive electrode thing by adhesive resin, positive electrode active materials and electric conducting material are mixed with known mixing ratio according to positive pole of the present invention, and this doping in positive electrode thing is coated on the anode collection device prepares.
Anodal attenuate is had no particular limits, still preferably pass through on anode collection device such as aluminium foil, to form positive pole, by the rolling method of use applicator roll, the screen cloth rubbing method, the knife coating of use scraper, spin-coating method, the knife coating of use drawdown rod is so that its thickness is even.
Negative pole 2 preferably upward or on each surface of preceding and rear surface prepares by any surface that the negative pole alloy is coated in negative pole currect collecting device 2a.This negative pole alloy contains adhesive resin and negative active core-shell material.Should be noted that as adhesive resin, can use to be used for anodal same material.
Negative pole currect collecting device 2a can be made by the material that is selected from copper, stainless steel and nickel.In these materials, consider that from performance and economic favourable angle copper is preferred.The shape of current collector is not particularly limited.For example, this current collector can use paper tinsel, wire netting, plate, foam, wool fabric, three-dimensional structure, as shapes such as nets.
Negative active core-shell material can suitably be selected according to the purposes of electrode or the kind of battery.The example of negative active core-shell material that is used for the negative pole of lithium secondary battery can comprise: alkali metal, alkali metal alloy, material with carbon element and those same materials as positive electrode active materials.
Alkali-metal example can comprise: Li, Na and K; The example of alkali metal alloy can comprise: lithium alloy, and as Li-Al, Li-Mg and Li-Al-Ni, and sodium alloy, as Na-Hg and Na-Zn.
The example of material with carbon element can comprise: graphite, carbon black, coke, vitreous carbon, carbon fiber and its sintered body.
The example that is used for the negative active core-shell material of lithium ion secondary battery negative pole is can reversibly store/discharge the material of lithium ion, as be difficult to graphited material with carbon element or graphite-based carbon material.More particularly, the example of this kind material with carbon element can comprise: the RESEARCH OF PYROCARBON material, coke (pitch coke, needle coke, petroleum coke), graphite material, the vitreous carbon material, the sintered body of organic polymer (by sintering phenol resin or furane resins etc. under proper temperature so that resin, carbon fiber or active carbide obtain).In addition, high polymer such as polyacetylene or polypyrrole or such as SnO 2Oxide also can be used as the material that can reversibly store/discharge lithium ion.
Can form the negative pole alloy by adhesive resin, negative active core-shell material and solvent are mixed with known mixing ratio according to negative pole of the present invention, and this negative pole alloy is coated on the negative pole currect collecting device prepares.
The negative pole attenuate is had no particular limits, still preferred rolling method by the use applicator roll, the screen cloth rubbing method, the knife coating of use scraper, spin-coating method, the knife coating of use drawdown rod is so that the thickness of negative pole is even.
Barrier film 3 is film formed by the resin with hole of guaranteeing ion permeability.Barrier film 3 preferable configuration are for turn-offing barrier film, and its fusion at high temperature is so that pore closure, thereby lose ion permeability.
Also can use the barrier film that does not have closing function.
Being used to form barrier film 3 examples of material can comprise: fluorine-based polymer, polyethers, for example poly(ethylene oxide) or PPOX, polyolefin, for example polyethylene, or polypropylene, polyacrylonitrile, polyvinylidene chloride, polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate, PVP, polyaziridine, polybutadiene, polystyrene, polyisoprene and its derivative.These materials can use separately or be used in combination with two or more.Particularly, preferably with the material of fluorine-based polymer as the formation barrier film.
The example of fluorine-based polymer can comprise: polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (HFP) copolymer [P (VDF-HFP)], vinylidene fluoride-trifluoro ethlyene dichloride (CTFE) copolymer [P (VDF-CTFE)], vinylidene fluoride-hexafluoropropylene fluoro rubber [P (VDF-HFP)], vinylidene fluoride-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) fluorubber [P (VDF-TFE-HFP)], and vinylidene fluoride-tetrafluoroethylene-perfluoroalkyl vinyl ether fluorubber.The vinylidene fluoride based polyalcohol preferably contains 50 quality % or more, particularly 70 quality % or more (upper limits: vinylidene fluoride about 97 quality %).Particularly, preferably use polyvinylidene fluoride (PVDF), vinylidene difluoride-hexafluoropropylene copolymer [P (VDF-HFP)] and vinylidene fluoride-trifluoro ethlyene dichloride copolymer [P (VDF-CTFE)].Preferred copolymerisation is because of the degree of crystallinity step-down, so that electrolyte is easy to dipping and make electrolyte be easy to keep.According to the present invention, not only have the high polymer of high-expansion, and high polymer such as PVDF with low bulk also can be used as the material that forms barrier film.
Be used for barrier film fluorine-based polymer weight average molecular weight 500000 or higher scope in, be preferably 500000～2000000, more preferably 500000～1500000.If this weight average molecular weight is too small, the obvious variation of the physical strength of barrier film then.Consequently, barrier film can be perforated or break, thereby can not have the function of separation.
Can add filler to the barrier film that is used for battery of the present invention.This filler has no particular limits on shape, diameter, density and the surface state of type (inorganic or organic) and physical property such as filler particles, as long as the particle of this filler can form matrix with the polymer of forming barrier film, can allow the hole of electrolyte-impregnated between filler and high polymer granule boundary to get final product to form.Example as the inorganic material powders of filler can comprise: oxide powder, carbonate powder and sulfate powder, as silica, titanium oxide, aluminium oxide, zinc oxide, calcium carbonate, calcium sulfate, tin oxide, chromium oxide, iron oxide, magnesium oxide, magnesium carbonate and magnesium sulfate, with other carbide, as carborundum and calcium carbide, and nitride, as silicon nitride and titanium nitride.Example as the organic substance powder of filler can comprise: with the inconsistent various types of polymer beads of matrix of the polymer of forming barrier film.
The particle diameter of filler particles has no particular limits, but can be preferably 0.005～1 μ m, more preferably 0.01～0.8 μ m in 10 μ m or littler scope.Add the amount of filler in polymer, depend on the type of polymer and the type of filler, this addition can be preferably 30～100 mass parts in 5～100 mass parts scopes, based on the polymer calculating of 100 mass parts.
Barrier film according to the present invention be by with polymer dissolution in solvent, and as required with fillers dispersed in solvent, slurry prepares to form.This solvent can suitably be selected from can various types of solvents of dissolve polymer, and consider from the industrialization angle, is preferably to have higher boiling point and high security.The example of solvent can comprise: N, dinethylformamide (DMF), dimethylacetylamide, N-methyl pyrrolidone, acetone, methylethylketone (MEK) and methyl iso-butyl ketone (MIBK).Polymer phase is preferably 5～25% (quality) for the concentration of solvent.
Replacement adds filler to form barrier film of the present invention in polymer, can adopt in polymer the method that adds plasticizer, and forms at polymer and this plasticizer to be come together after membranaceous.The example of this plasticizer can comprise: dimethyl adipate; diisobutyl adipate; dibutyl adipate; adipic acid two-2-ethylhexyl; diisodecyl adipate (DIDA); adipic acid dibutyl diol ester, two-2-ethylhexyl azelate, dimethyl sebacate; dibutyl sebacate; two-2-ethylhexyl sebacate, acetyl group castor oil acid methyl esters, repefral; diethyl phthalate; dibutyl phthalate, dibutyl phthalate (DHP), two-2-ethylhexyl phthalic acid ester; two-just-octyl group phthalic acid ester; diisooctyl phthalate, butyl benzyl phthalate, phthalic acid diisononyl esters and ethyl phthalyl ethyl glycinamide carboxylic ester.In these materials, consider that from the angle that is used to the work of extracting dibutyl phthalate and phthalic acid dioctyl ester are preferred the uses.The addition of plasticizer is 10～200 mass parts, based on the polymer calculating of 100 mass parts.
Barrier film is arranged between positive pole and the negative pole, and is assembled in the battery in this manner.More particularly, form membranaceous barrier film be retained between positive pole and the negative pole and form with it by applied pressure between positive pole and the negative pole whole, thereby prepare element cell; Perhaps the barrier film of slurry form is coated between positive pole and the negative pole, makes barrier film sclerosis by heating subsequently, and anodal and negative pole is overlapped, to make element cell.
Secondly, as shown in Figure 3, so the element cell T that obtains is stacked each other on together, and the electrode body 8 of two one-sided coatings is placed the highest and lowest side of this element cell T heap, so that form battery structure group M.This battery structure group M is contained in battery case 6 as in battery container or the laminate packaging, and fills this battery case 6 with electrolyte.Then,, then it is carried out seal of vessel,, then carry out heat seal, on the outer surface of battery case 6, cover extensible high polymer sheet 7 of the present invention subsequently if perhaps its structure is a laminate packaging if the structure of this battery case 6 is battery containers.Obtained lithium-base battery of the present invention thus.
The used electrolyte of lithium-base battery of the present invention is to prepare by ionic conduction salt is dissolved in the solvent that can dissolve this ionic conduction salt.
Ionic conduction salt has no particular limits, and can be to be used for those of conventional lithium-base battery.The example of ionic conduction salt can comprise: LiClO 4, LiBF 4, LiAsF 6, LiPF 6, LiSbF 6, LiCF 3SO 3, LiCF 3COO, NaClO 4, NaBF 4, NaSCN, KBF 4, Mg (ClO 4) 2, Mg (BF 4) 2, (C 4H 9) 4NBF 4, (C 2H 5) 4NBF 4, (C 4H 9) 4NClO 4, LiN (CF 3SO 2) 2(C 2H 5) 4NPF 6These materials can use separately or two or more are used in combination.
The example that can dissolve the solvent of above-mentioned ionic conduction salt can comprise: chain ether, as dibutyl ethers, 1,2-dimethoxy-ethane, 1,2-ethyoxyl methoxy base ethane, methyl diethylene glycol dimethyl ether, methyl triglyme, methyl tetraethylene glycol dimethyl ether, ethyl glycinamide diethylene glycol dimethyl ether (ethylglyme), ethyl diethylene glycol dimethyl ether, butyldiglycol dimethyl ether or glycol ether (ethyl cellosolve, ethyl carbitol, butyl cellosolve or butyl carbitol); Heterocyclic ether is as oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes or 4,4-dimethyl-1,3-diox; Butyrolactone, as gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi, 3-methyl isophthalic acid, 3-oxazolidine-2-ketone or 3-ethyl-1,3-oxazolidine-2-ketone; And other is usually used in the solvent of lithium-base battery, as water, alcoholic solvent (methyl alcohol, ethanol, butanols, ethylene glycol, propylene glycol, diethylene glycol (DEG), 1, the 4-butanediol, glycerine etc.), polyoxyalkylene-polyol solvent (poly(ethylene oxide), PPOX, polyoxyethylene-oxypropylene glycol etc., they can two or more be used in combination), amide solvent (N-methylformamide, the N-N-dimethyl formamide, the N-methylacetamide, N-methylpyrrole alkanol (pyrrolidinone) etc.), carbonate solvent (diethyl carbonate, dimethyl carbonate, the ethylene methyl esters, propylene carbonate, ethylene carbonate, carbonic acid styrene esters (styrene carbonate) etc.), and imidazolidinone solvent (1,3-dimethyl-2-imidazolidinone etc.).These materials can use separately or two or more are used in combination.Particularly, preferred carbonate group solvent is as nonaqueous solvents, for example propylene carbonate.In addition, in solvent, the concentration of ionic conduction salt is about 0.5～1.5 mol.
Beyond the deionization conducting salt, this electrolyte can contain and has at least one, is preferably the compound of at least two reactive double bonds.This compound that contains reactive double bond reacts with the formation tridimensional network, thereby forms gel-form solid polymer electrolyte.
The illustrative example that contains the reactive double bond compound comprises: the compound with two or more reactive double bonds, as divinylbenzene, divinylsulfone, ALMA, Ethylene glycol dimethacrylate, dimethacrylate diethylene glycol (DEG) ester, the dimethacrylate triethyleneglycol ester, poly dimethyl acrylic acid glycol ester (mean molecule quantity is 200～1000), 1, the 3-butanediol dimethylacrylate, 1, the 6-hexanediol dimethacrylate, the dimethacrylate DOPCP, poly dimethyl acrylic acid propylene glycol ester (mean molecule quantity is 400), 2-hydroxyl-1,3-dimethyl allene acyloxy propane, 2, two [4 (methacryloxy ethyoxyl) phenyl] propane of 2-, 2, two [4-(methacryloxy ethyoxyl-diethoxy) phenyl] propane of 2-, 2, two [4-(methacryloxy ethyoxyl-polyethoxy) phenyl] propane of 2-, ethylene glycol diacrylate, diacrylate diethylene glycol (DEG) ester, the diacrylate triethyleneglycol ester, poly-ethylene glycol diacrylate (mean molecule quantity is 200～1000), 1, the 3-butanediol diacrylate, 1, the 6-hexanediyl ester, diacrylic acid pentyl diol ester, poly-diacrylate propylene glycol ester (mean molecule quantity is 400), 2-hydroxyl-1,3-two propylene acyloxy propane, 2, two [4 (acryloyl-oxy base oxethyl) phenyl] propane of 2-, 2, two [4-(acryloyl-oxy base oxethyl-diethoxy) phenyl] propane of 2-, 2, two [4-(acryloyl-oxy base oxethyl-polyethoxy) phenyl] propane of 2-, trihydroxy methyl-propane triacrylate, trimethylol-propane trimethacrylate, the tetramethylol methane triacrylate, the tetramethylol methane tetraacrylate, the soluble polyurethane diacrylate, water-soluble poly propylhomoserin dimethylacrylate, tristane dimethanol acrylate, hydrogenation bicyclopentadiene diacrylate (hydrogenated dicyclopentadienediacrylate), polyester diacrylate and polyester dimethylacrylate.
If desired, can add the compound that contains acrylic acid groups or methacrylic acid group.The example of this kind compound comprises: acrylate and methacrylate; as glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, methoxyl group diethylene glycol (DEG) methacrylate, methoxyl group triethylene glycol methacrylate and methoxyl group-polymethylacrylic acid glycol ester (mean molecule quantity is 200～1200); and methacryl based isocyanate, 2-hydroxyl-methyl acrylic acid and N, N-dimethyl aminoethyl methacrylic acid.Also can add the compound that other contains reactive double bond, as acrylamide (for example, N-methylol-acrylamide, methylene-bisacrylamide, DAAM), and vinyl compound, as Yi Xi oxazolin and vinylene carbonate.
In order to form tridimensional network, must add compound with at least two reactive double bonds.Just, tridimensional network can not only prepare with compound such as methyl methacrylate with single reactive double bond.Need to add some and have the compound of at least two reactive double bonds.
In the above-mentioned compound with reactive double bond, particularly preferred reactive monomer comprises: the diester that contains the polyoxyalkylene component of following general formula (1).Suggestion is used in combination the latter with the monoester compound that contains the polyoxyalkylene component and three ester compounds of following general formula (2).
Figure A0113724700191
In general formula (1), R 1, R 2And R 3Independent respectively for hydrogen atom or have 1～6 carbon atom and be preferably the alkyl of 1～4 carbon atom, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group; And X and Y satisfy condition: X 〉=1 and Y 〉=0, or full X 〉=0 and Y 〉=1.The value of X+Y preferably is not higher than 100, in particular for 1～30.R 1, R 2And R 3Most preferably be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group.
Figure A0113724700201
In general formula (2), R 4, R 5And R 6Independent respectively for hydrogen atom or have 1～6 carbon atom and be preferably the alkyl of 1～4 carbon atom, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group; And A and B foot bar: A 〉=1 and B 〉=O, or satisfy condition: A 〉=O and B 〉=1.The value of A+B preferably is not higher than 100, in particular for 1～30.R 4, R 5And R 6Most preferably be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group.
Wherein, the diester of general formula (1), X=9 wherein, Y=0, and R 1=R 3=CH 3Be preferred, the monoesters of general formula (2), A=2 or 9 wherein, B=0, and R 4=R 6=CH 3Be preferred.
Trimethylol-propane trimethacrylate is typical three ester compounds.
Usually, heating is at the diester that contains the polyoxyalkylene component described in the electrolyte composition and describedly contain the monoesters and described three esters of polyoxyalkylene component or (for example make its radiation that is exposed to appropriate format, the radiation of electron beam, microwave or radio frequency) in, or the mixture of heating diester and monoesters, to form tridimensional network.
The tridimensional network normally diester by only will containing the polyoxyalkylene component and the reaction of three esters forms., such just as has been noted, preferably the monoesters that contains the polyoxyalkylene component with monofunctional monomer joins in the diester and three esters of polyfunctional monomer, and its reason is that this interpolation is incorporated into the polyoxyalkylene side chain in the three-dimensional network.
Herein, the diester that contains the polyoxyalkylene component does not have strict restriction with the relative scale of monoesters that contains polyoxyalkylene and three ester compounds, and can suitably determine according to the length of polyoxyalkylene component.Consider that from the angle that gel strength strengthens the ratio of preferred diester compound and monoester compound drops in 0.1～2 the scope, particularly 0.3～1.5, and the weight ratio of diester compound and three ester compounds drops in 2～15 the scope, particularly 3～10.
According to lithium-base battery of the present invention, as shown in figure 15, even metal bar 9 pierces through the battery case (not shown) as nail and penetrates the positive pole 1 that stacks together by barrier film 3 and during negative pole 2 from the external world, the extensible high polymer sheet 7 of clad battery container (not shown) outer surface also will extend along metal bar 9, thereby cover the side surface of metal bar 9, so that so the high polymer sheet 7 with suitable low conductivity that extends is inserted between metal bar 9 and positive pole 1 and the negative pole 2, and between metal bar 9 and anode collection device 1a and negative pole currect collecting device 2a.Consequently, can effectively prevent big short circuit current by metal bar 9 and anodal 1 and negative pole 2 between flow, thereby prevented to make battery be in the high temp/high pressure state, and prevented explosion and/or light in moment.
Therefore even battery is crashed by powerful external force, and barrier film is when breaking and since extensible high polymer sheet 7 be inserted in anodal 1 and negative pole 2 between, thereby may prevent anodal 1 and negative pole 2 owing to being in contact with one another the internal short-circuit that causes.
In addition, according to the present invention, because the outer surface of battery case covers with extensible high polymer sheet, the turning and the surface of battery are protected equally.
Though first embodiment of the present invention is described, the present invention is not limited to this, and is to be understood that and carries out various changes and do not depart from scope of the present invention.
＜the second embodiment 〉
Fig. 4 is the schematic cross-section according to the battery structure group M of the lithium-base battery of second embodiment of the invention.The lithium-base battery of this embodiment comprises: the battery structure group, this electricity structural group is made by stacked unit cells T, each element cell T comprises positive pole 1, negative pole 2 and insertion barrier film 3 therebetween, and electrolyte, wherein the periphery of battery structure group M be coated with stretch percentage elongation be 1% or higher ion do not see through and extendible high polymer sheet 7.
In such cases, after the periphery of battery structure group M covers with extensible high polymer sheet, electrolyte can be injected or pours into battery.Alternately, electrolyte can inject the battery structure group in advance, then covers the periphery of this battery structure group with extensible high polymer sheet.
In second embodiment, extensible high polymer sheet 7 can with first embodiment in identical, and other parts are also identical with corresponding component in first embodiment, therefore these parts are represented by the reference number identical with the first embodiment corresponding component, and have omitted the explanation that repeats.
As shown in Figure 5, can improve, extensible high polymer sheet 7 is arranged on the highest and minimum surface of battery structure group M second embodiment.Can also improve second embodiment, (just, elongated element cell T) integral body is reeled according to the direction shown in Fig. 6 A, to form battery structure group M with element cell T, and shown in Fig. 6 B, cover the outer surface of this battery structure group M with extensible high polymer sheet 7 of the present invention.Though not shown, elongated element cell T can be folding, to make battery structure group M.
Second embodiment can combine according to following method with first embodiment: promptly, as shown in Figure 7, the periphery stretch percentage elongation of battery structure group M is 1% or higher ion does not see through and extensible high polymer sheet covers, and the outer surface of battery case 6 is 1% or higher ion does not see through and extensible high polymer sheet covers with stretch percentage elongation also, with further raising fail safe.
Lithium-base battery according to second embodiment of the invention, because the extensible high polymer sheet of the outer periderm of this battery structure group covers, even when therefore causing meeting accident accident owing to outside cause, when for example even nail pierces through battery or cell fracture, effective deformation also can take place in this high polymer sheet between positive pole and negative pole, thereby prevent that big electric current from flowing between electrode, thereby prevented that battery moment is in the high temp/high pressure state, thereby prevent explosion and/or light.And because the extensible high polymer sheet of the outer periderm of battery structure group covers, this battery structure group can advantageously be fixed.
Though second embodiment of the present invention is described, the present invention is not limited to this, be to be understood that various changes all do not depart from scope of the present invention.
＜the three embodiment 〉
Fig. 8 and 9 is the sectional views according to the lithium-base battery of third embodiment of the invention.The structure of this lithium-base battery can make by piling up the battery structure group that 3 element cell T make and be contained in the battery case (not shown), and this battery is filled with electrolyte, and wherein each element cell T comprises anodal 1, negative pole 2 and inserts therebetween barrier film 3.
In such cases, as shown in figure 10, the positive pole 1 of element cell T and negative pole 2 form on the surface of anode collection device 1a and negative pole currect collecting device 2a respectively, and make them pass through therebetween barrier film mutually in the face of being provided with.In other words, the positive pole 1 of element cell T is arranged as back-to-back, and similarly negative pole 2 also is arranged as back-to-back.And, as shown in Figure 8, by stacked unit cells T 1, T 2And T 3The outer surface of the battery structure group that the forms elongation that is stretched is 1% or higher ion does not see through and extendible high polymer sheet 7 covers.Alternately, in Fig. 8, element cell T 1, T 2And T 3Be arranged as identical polar overlap (just, anodal 1 do not overlap on the negative pole 2).
In addition, as shown in Figure 9, stretch percentage elongation is 1% or higher ion does not see through and extendible high polymer sheet 7 can be arranged between two adjacent element cell T, and on the highest and minimum surface of the battery structure group that forms of stacked unit cells.
In the 3rd embodiment, extensible high polymer sheet 7 can with first embodiment in identical, and other parts also can be identical with the corresponding component in first embodiment, therefore these parts use the reference number identical with corresponding component in first embodiment to represent, and have omitted repeat specification.
Shown in Figure 11 A～11C, the lithium-base battery in the 3rd embodiment can be for convoluted, and wherein integral body of element cell (elongated element cell just) or battery structure group can be for reeling.
In the lithium-base battery shown in Figure 11 A, extensible high polymer sheet 7 is arranged on the back of the body surface of elongated element cell, and this elongated element cell is reeled according to direction shown in the arrow among the figure.This in such cases, extensible high polymer sheet can be arranged in the top surface of elongated element cell, and the position between positive pole and negative pole relation is reversible.
In the lithium-base battery shown in Figure 11 B, extensible high polymer sheet 7 is arranged between two elongated element cells, and this elongated element cell is reeled according to the direction shown in arrow among Figure 11 B.In such cases, this elongated element cell T must arrange in the following manner that promptly identical polar stacks together mutually, and extensible high polymer sheet 7 is set therebetween.This extensible high polymer sheet can be arranged on the highest face temperature and/or minimum surface that piles up the battery structure group that the elongated element cell makes.In such cases, anodal and negative pole can be arranged as stacked mutually.
In the lithium-base battery shown in Figure 11 C, extensible high polymer sheet 7 is arranged between the elongated element cell, and be arranged in by on the minimum surface that piles up the battery structure group M that the elongated element cell forms, battery structure group M reels according to the direction shown in the arrow among the figure.In such cases, this high polymer sheet can be arranged on the top surface of battery structure group M.In addition, in Figure 11 B and 11C, omitted lead-in wire thin slice (tab).The quantity of the elongated element cell that piles up has no particular limits, but is generally 2～20.Though not shown, certainly folding by the battery structure group of piling up above-mentioned elongated element cell formation.
The 3rd embodiment can combine according to following method with first and second embodiments: promptly, stretch percentage elongation be 1% or higher ion does not see through and extendible high polymer sheet can form between the element cell and/or outer surface at each element cell on form; The periphery of the battery structure group of making by stacked unit cells or integral body folding or the winder unit battery can be 1% or higher ion does not see through and extendible high polymer sheet covers with stretch percentage elongation; And the outer surface that wherein accommodates the battery case of battery structure group or element cell can be 1% or higher ion does not see through and extendible high polymer sheet covers with this stretch percentage elongation.Adopt this kind structure, can further improve the fail safe of lithium-base battery.
Lithium-base battery according to the 3rd embodiment, because extensible high polymer is arranged between two adjacent element cells and/or is arranged on the outer surface of each element cell (or periphery of battery structure group), even when causing meeting accident accident owing to outside cause, when for example even nail pierces through battery or battery crushing, deformation effectively also can take place in this high polymer between positive pole and negative pole, thereby prevent that big electric current from flowing between electrode, and prevented that battery moment is in the high temp/high pressure state, and thereby prevented explosion and/or lighted.In addition, because the outer surface of each element cell covers with the high polymer sheet, therefore can fix each element cell exactly, and can any deviation not take place with reference position.
Though the 3rd embodiment of the present invention is described, the present invention is not limited to this, should be appreciated that and to carry out various changes and do not depart from scope of the present invention.
According to lithium-base battery of the present invention, because battery comprises the extensible high polymer sheet with high stretch percentage elongation, even when therefore causing meeting accident accident owing to outside cause, when for example even nail pierces through battery or cell fracture, can prevent effectively that also big electric current from flowing between positive pole and negative pole, thereby guarantee higher fail safe.
The shape preferable configuration of lithium-base battery of the present invention is a stacked as shown in figure 12; Yet the present invention is not limited to this.For example, the shape of lithium-base battery of the present invention also can be configured to folded form as shown in figure 13, and as shown in figure 14 convoluted, and also can be configured to Coin shape is square or have the cylindrical etc. of helical structure.
As mentioned above, lithium-base battery of the present invention has excellent characteristic, as high security, and thereby be applicable to various uses, for example as the television camera portable terminal device, notebook personal computer, portable phone, the main power source of PHSs or the like, the stand-by power supply of memory, power supply during PC moment power cut-off, the power supply of electric motor car or motor vehicle driven by mixed power, and combine with solar cell and to be used in the solar energy generated energy stocking system.

Claims (6)

1, a kind of lithium-base battery comprises:
The battery structure group, this battery structure group is made by stacked unit cells, and each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film, perhaps the integral body preparation by folding or the described element cell of reeling;
Battery case is used to hold described battery structure group; And
Electrolyte after described battery structure group is installed in the described battery case, is injected in the described battery case;
The outer surface stretch percentage elongation of wherein said battery case is 1% or higher ion does not see through and extendible high polymer sheet covers.
2, a kind of lithium-base battery comprises:
The battery structure group, this battery structure group is made by stacked unit cells, and each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film, perhaps the integral body preparation by folding or the described element cell of reeling; With
Electrolyte;
The periphery stretch percentage elongation of wherein said battery structure group is 1% or higher ion does not see through and extendible high polymer sheet covers.
3, a kind of lithium-base battery comprises:
The battery structure group, this battery structure group is made by stacked unit cells, and each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film, perhaps the integral body preparation by folding or the described element cell of reeling;
Battery case is used to hold described battery structure group; And
Electrolyte after described battery structure group is installed in the described battery case, is injected in the described battery case;
The outer surface stretch percentage elongation of wherein said battery case is 1% or higher ion does not see through and extendible high polymer sheet covers, and the also described ion of the periphery of described battery structure group does not see through and extendible high polymer sheet covers.
4, a kind of lithium-base battery comprises:
The battery structure group, this battery structure group is made by stacked unit cells, and each element cell comprises positive pole, negative pole and is arranged at therebetween barrier film, perhaps the integral body preparation by folding or the described element cell of reeling;
Battery case is used to hold described battery structure group; And
Electrolyte after described battery structure group is installed in the described battery case, is injected in the described battery case;
Wherein the described positive pole of each described element cell and described negative pole respectively on a surface of anode collection device and negative pole currect collecting device so that its opposed facing mode forms, and described barrier film is arranged at therebetween; And
Arrange between two adjacent described element cells and/or on the outer surface at each described element cell stretch percentage elongation be 1% or higher ion do not see through and extendible high polymer sheet.
5, according to each lithium-base battery of claim 1～3, wherein the described positive pole of each described element cell and described negative pole respectively on a surface of anode collection device and negative pole currect collecting device so that its opposed facing mode form.And described barrier film is arranged at therebetween; And
Arrange between two adjacent described element cells and/or on the outer surface at each described element cell stretch percentage elongation be 1% or higher ion do not see through and extendible high polymer sheet.
6, according to each lithium-base battery in the claim 1～5, wherein said extensible high polymer sheet is selected from by at least a: polyamide-based elastomer, polyurethane-base elastomer, polyolefin-based elastomer, polyester-based elastomer, styrene-based elastomer, chlorovinyl elastomer and fluorine-based elastomeric material are made.
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